Sulfonylureas

ABSTRACT

N-Phenylsulfonyl-N&#39;-pyrimidinyl-,-N&#39;-triazinyl- and-N&#39;-triazolylureas and -thioureas of formula I ##STR1## in which X is oxygen, sulfur, SO or SO 2  ; W is oxygen or sulfur, R 1  is hydrogen or methyl; R 2  is hydrogen, fluorine, chlorine, bromine, iodine, (X) n  R 3 , NO 2 , NR 4  R 5 , --C.tbd.CR 6 , ##STR2## or cyano; n is the number 0 or 1; R 3  is C 1  -C 4  alkyl or C 1  -C 4  alkyl which is substituted by 1-4 halogen atoms, C 1  -C 3  alkoxy or C 1  -C 3  alkylthio; or C 2  -C 4  alkenyl or C 2  -C 4  alkenyl which is substituted by 1-4 halogen atoms; R 4  is hydrogen, CH 3  O, CH 3  CH 2  O or C 1  -C 3  alkyl; R 5  is hydrogen or C 1  -C 3  alkyl; R 6  is hydrogen, methyl or ethyl; R 7  is hydrogen or methyl; Z is ##STR3## E is methine or nitrogen; R 8  is C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, C 1  -C 4  haloalkyl, C 1  -C 4  haloalkylthio, C 1  -C 4  alkylthio, halogen, C 2  -C 5  alkoxyalkyl, C 2  -C 5  alkoxyalkoxy, amino, C 1  -C 3  alkylamino or di(C 1  -C 3  alkyl)amino; R 9  is C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, C 1  -C 4  haloalkylthio, C 1  -C 4  alkylthio, C 2  -C 5  alkoxyalkyl, C 2  -C 5  alkoxyalkoxy, C 2  -C 5  alkylthioalkyl or cyclopropyl; R 10  is hydrogen, fluorine, chlorine, methyl, trifluoromethyl, CH 3  O, CH 3  CH 2  O, CH 3  S, CH 3  SO, CH 3  SO 2  or cyano; R 11  is methyl, ethyl, CH 3  O, CH 3  CH 2  O, fluorine or chlorine; R 12  is methyl, ethyl, CH 3  O, CH 3  CH 2  O, fluorine or chlorine; R 13  is C 1  -C 3  alkyl; and R 14  is C 1  -C 3  alkyl, C 1  -C 3  alkoxy, chlorine or OCHF.sub. 2 ; and the salts of these compounds; with the provisos that E is methine if R 8  is halogen; and E is methine if R 8  or R 9  is OCHF 2  or SCHF 2 , and the salts of these compounds with amines, alkali metal or alkaline earth metal bases or quaternary ammonium bases have good pre- and postemergence selective herbicidal and growth-regulating properties.

This is a division of Ser. No. 08/419,307 filed Apr. 10, 1995, which isa continuation of Ser. No. 08/373,713, filed Jan. 17, 1995, nowabandoned, which is a division of Ser. No. 08/154 768, filed Nov. 19,1993, now U.S. Pat. No. 5,412,107, which is a division of Ser. No.08/014,947, filed Feb. 8, 1993, now U.S. Pat. No. 5,286,709, which is adivision of Ser. No. 07/823,515, filed Jan. 21, 1992, now U.S. Pat. No.5,209,771.

The present invention relates to novel, herbicidally active and plantgrowth-regulating N-phenylsulfonyl-N'-pyfimidinyl-,-N'-triazinyl-and-N'-triazolylureas and-thioureas, processes for their preparation,compositions containing them as active ingredients, and their use forcontrol of weeds, in particular selectively in crops of useful plants,or for regulating and inhibiting plant growth.

Urea compounds, triazine compounds and pyrimidine compounds having aherbicidal action are generally known. Such compounds are described, forexample, in European Patent Applications 0 007 687, 0 030 138, 0 073 562and 0 126 711.

Novel sulfonylureas and-thioureas having herbicidal and plantgrowth-regulating properties have now been found.

The N-phenylsulfonyl-N'-pyrimidinyl,-N'-triazinyl- and-N'-triazolylureasand-thioureas according to the invention are those of the formula I##STR4## in which X is oxygen, sulfur, SO or SO₂ ; W is oxygen orsulfur, R₁ is hydrogen or methyl; R₂ is hydrogen, fluorine, chlorine,bromine, iodine, (X)_(n) R₃, NO₂, NR₄ R₅ --C.tbd.CR₆, ##STR5## or cyano;n is the number 0 or 1; R₃ is C₁ -C₄ alkyl or C₁ -C₄ alkyl which issubstituted by 1-4 halogen atoms, C₁ -C₃ alkoxy or C₁ -C₃ alkylthio; orC₂ -C₄ alkenyl or C₂ -C₄ alkenyl which is substituted by 1-4 halogenatoms; R₄ is hydrogen, CH₃ O, CH₃ CH₂ O or C₁ -C₃ alkyl; R₅ is hydrogenor C₁ -C₃ alkyl; R₆ is hydrogen, methyl or ethyl; R₇ is hydrogen ormethyl; Z is ##STR6## E is methine or nitrogen; R₈ is C₁ -C₄ alkyl, C₁-C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkylthio,C₁ -C₄ alkylthio, halogen, C₂ -C₅ alkoxyalkyl, C₂ -C₅ alkoxyalkoxy,amino, C₁ -C₃ alkylamino or di(C₁ -C₃ alkyl)amino; R₉ is C₁ -C₄ alkyl,C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ haloalkylthio, C₁ -C₄alkylthio, C₂ -C₅ alkoxyalkyl, C₂ -C₅ alkoxyalkoxy, C₂ -C₅alkylthioalkyl or cyclopropyl; R₁₀ is hydrogen, fluorine, chlorine,methyl, trifiuoromethyl, CH₃ O, CH₃ CH₂ O, CH₃ S, CH₃ SO, CH₃ SO₂ orcyano; R₁₁ is methyl, ethyl, CH₃ O, CH₃ CH₂ O, fluorine or chlorine; R₁₂is methyl, ethyl, CH₃ O, CH₃ CH₂ O, fluorine or chlorine; R₁₃ is C₁-C.sub. 3 alkyl; and R₁₄ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy, chlorine orOCHF₂ ; and the salts of these compounds; with the provisos that E ismethine if R₈ is halogen; and E is methine if R₈ or R₉ is OCHF₂ orSCHF₂.

In the above definitions, halogen is to be understood as meaningfluorine, chlorine, bromine or iodine, preferably fluorine, chlorine orbromine.

The alkyl groups in the substituent definitions can be straight-chain orbranched and are, for example, methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl or ten-butyl. The alkyl groups occurring asor in the substituents preferably have 1-3 carbon atoms.

Alkenyl is to be understood as meaning straight-chain or branchedalkenyl, for example vinyl, allyl, methallyl, 1-methylvinyl orbut-2-en-1-yl. Alkenyl radicals having a chain length of 2 to 3 carbonatoms are preferred.

Haloalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl or2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,trifluoromethyl or dichlorofluoromethyl.

Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy,n-butyloxy, isobutyloxy, sec-butyloxy or tert-butyloxy; preferablymethoxy or ethoxy.

Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy,2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy,2-chloroethoxy or 2,2-difluoroethoxy; preferably difluoromethoxy,2-chloroethoxy or trifluoromethoxy.

Alkylthio is, for example, methylthio, ethylthio, propylthio,isopropylthio, n-butylthio, iso-butylthio, sec-butylthio orten-butylthio, preferably methylthio or ethylthio.

Examples of alkoxyalkoxy are: methoxymethoxy, methoxyethoxy,methoxypropyloxy, ethoxymethoxy, ethoxyethoxy or propyloxymethoxy.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino orisopropylamino. Dialkylamino is, for example, dimethylamino,methylethylamino, diethylamino or n-propylmethylamino.

The invention also relates to the salts which the compounds of theformula I can form with amines, alkali metal and alkaline earth metalbases or quatemary ammonium bases.

Preferred alkali metal and alkaline earth metal hydroxides assalt-forming agents are the hydroxides of lithium, sodium, potassium,magnesium or calcium, in particular those of sodium or potassium.

Examples of amines which are suitable for salt formation are primary,secondary and tertiary aliphatic and aromatic amines, such asmethylamine, ethylmine, propylamine, isopropylamine, the four isomericbutylamines, dimethylamine, diethylamine, diethanolamine, dipropylamine,diisopropylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine,trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine,quinoline and isoquinoline, in particular ethyl-, propyl-, diethyl- ortriethylamine, especially isopropylamine and diethanolamine.

Examples of quaternary ammonium bases are in general the cations ofhaloammonium salts, for example the tetramethylammonium cation, thetrimethylbenzylammonium cation, the triethylbenzylammonium cation, thetetraethylammonium cation, the trimethylethylammonium cation or even theammonium cation.

Preferred compounds of the formula I are those in which W is oxygen, Zis preferably Z1, X is oxygen or sulfur, but particularly preferablyoxygen, and E is nitrogen.

A preferred group of compounds of the formula I is furthermore that inwhich Z is Z1 and X is oxygen or sulfur, particularly preferably oxygen,and E is methine.

Compounds of these two groups of compounds of the formula I which are ofparticular interest are those in which R₂ is hydrogen, fluorine,chlorine, OCH₃, OCHF₂, methyl, SCH₃, methoxy, ethoxy or chloroethoxy; R₈is C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₂ haloalkoxy, trifluoromethyl,CHF₂, CH₂ F, CH₂ OCH₃, fluorine, chlorine, NH₂, NHCH₃, N(CH₃)₂, SCH₃ orCH₂ OCH₃ ; and R₉ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₂ haloalkoxy orcyclopropyl.

In particularly preferred compounds of this group, R₂ is hydrogen; R₈ ismethyl, ethyl, OCH₃, OC₂ H₅, OCHF₂, OCH₂ CF₃, chlorine, NHCH₃, N(CH₃)₂or CH₂ OCH₃ ; and R₉ is methyl, OCH₃, OCHF₂, OC₂ H₅ or cyclopropyl.

In another preferred sub-group of compounds of the formula I, W isoxygen; Z is Z1; X is sulfur; R₂ is hydrogen, fluorine, chlorine, OCH₃,OCHF₂, methyl or methylthio; R₈ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₂haloalkoxy, CF₃, CHF₂, CH₂ F, CH₂ OCH₃, fluorine, chlorine, NH₂, NHCH₃,N(CH₃)₂, SCH₃ or CH₂ OCH₃ ; and R₉ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁-C₂ haloalkoxy or cyclopropyl.

Compounds of the formula I from this group which are of interest arethose in which W is oxygen; Z is Z1; X is sulfur; R₂ is hydrogen; R₈ ismethyl, ethyl, OCH₃, OC₂ H₅, OCHF₂, OCH₂ CF₃, Cl, NHCH₃, N(CH₃)₂ or CH₂OCH₃ ; and R₉ is methyl, OCH₃, OCHF₂, OC₂ H₅ or cyclopropyl.

Preferred individual compounds from the scope of formula I are:

N-[2-(oxetan-3-oxycarbonyl)]phenylsulfonyl-N'-(4-methoxy-6-methyl-1,3,5-triazinyl)-urea;

N-[2-(oxetan-3-oxycarbonyl)]phenylsulfonyl-N'-(4,6-dimethylpyrimidin-2-yl)urea;

N-[2-(oxetan-3-oxycarbonyl)]phenylsulfonyl-N'-(4-methoxy-6-methylpyrimidin-2-yl)urea;and

N-[2-(oxetan-3-oxycarbonyl)]phenylsulfonyl-N'-(4,6-dimethoxypyrimidin-2-yl)urea.

The compounds of the formula I can be prepared by either

a) reacting a phenylsulfonamide of the formula II ##STR7## in which R₂and X are as defined under formula I, with an pyrimidinyl-, triazolyl-or triazinylcarbamate or -thiocarbamate of the formula III ##STR8## inwhich W, Z and R₁ are as defined under formula I and R₁₅ is phenyl orsubstituted phenyl, in the presence of a base, or

b) reacting a sulfonylcarbamate or -thiocarbamate of the formula IV##STR9## in which R₂, W, X and Z are as defined under formula I and R₁₅is as defined under formula III, with an amine of the formula V

    H.sub.2 N--Z                                               (V)

in which Z is as defined under formula I, in the presence of a base, or

c) reacting a phenylsulfonamide of the formula II ##STR10## in which R₂and X are as defined under formula I, with an pyrimidinyl-, triazolyl-or triazinyl isocyanate or isothiocyanate of the formula VII

    Y═N═C--Z                                           (VII)

in which Z is as defined under formula I and Y is oxygen or sulfur, inthe presence of a base.

Compounds of the formula I can also be prepared by reacting a compoundof the formula VIII with a compound of the formula V in the presence ofan ammonium-, phosphonium-, sulfonium- or alkali metal cyanate salt ofthe formula X

    M.sup.+ OCN.sup.-                                          (X)

wherein M is an alkali metal or the group R₁₅ R₁₆ R₁₇ R₁₈ Q, in whichR₁₅ R₁₆ R₁₇ R₁₈ independently from another is C₁ -C₁₈ -alkyl, benzyloder phenyl, with the total number of C-atoms not greater than 36; and Qis nitrogen, sulfur or phosphorus. According to this method thecompoundsN-[2-(oxetan-3-oxycarbonyl)]phenylsulfonyl-N'-(4-methoxy-6-methyl-1,3,5-triazinyl)-ureaN-[2-(oxetan-3-oxycarbonyl)]phenylsulfonyl-N'-(4,6-dimethylpyrimidin-2-yl)urea;N-[2-(oxetan-3-oxycarbonyl)]phenylsulfonyl-N'-(4-methoxy-6-methylpyrimidin-2-yl)urea;andN-[2-(oxetan-3-oxycarbonyl)]phenylsulfonyl-N'-(4,6-dimethoxypyrimidin-2-yl)ureacan be prepared with advantage. Such reactions are described in SwissPatent No. 662 348.

The reactions to give compounds of the formula I are advantageouslycarried out in aprotic, inert organic solvents. Such solvents arehydrocarbons, such as benzene, toluene, xylene or cyclohexane,chlorinated hydrocarbons, such as methylene chloride, chloroform, carbontetrachloride or chlorobenzene, ethers, such as diethyl ether, ethyleneglycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuranor dioxane, nitriles, such as acetonitrile or propionitrile, and amides,such as dimethylformamide, diethylformamide or N-methylpyrrolidone. Thereaction temperatures are preferably between -20° and +120° C.

The reactions in general proceed slightly exothermically and can becarried out at room temperature. The mixture is advantageously heated tothe boiling point of the reaction mixture for a short time for thepurpose of shortening the reaction time or to start the reaction. Thereaction times can also be shortened by addition of a few drops of baseas a reaction catalyst. Suitable bases are, in particular, tertiaryamines, such as trimethylamine, triethylamine, quinuclidine,1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or1,5-diazabicyclo[5.4.0]undec-7-ene. However, inorganic bases such ashydrides, such as sodium hydride or calcium hydride, hydroxides, such assodium hydroxide and potassium hydroxide, carbonates, such as sodiumcarbonate and potassium carbonate, or bicarbonates, such as potassiumbicarbonate and sodium bicarbonate, can also be used as bases.

The end products of the formula I can be isolated by concentrating themixture and/or evaporating off the solvent and purified byrecrystallisation or trituration of the solid residue in solvents inwhich they are not readily soluble, such as ethers, aromatichydrocarbons or chlorinated hydrocarbons.

In the preparation processes described above for compounds of theformula I, R₁₅ is preferably phenyl which can be substituted by C₁ -C₄alkyl or halogen, especially preferably phenyl.

The phenylsulfonamides of the formula II are novel compounds which havebeen developed and prepared specifically for the preparation of theactive ingredients of the formula I. The present invention thus alsorelates to them. They can be prepared from the correspondingphenylsulfonyl chlorides of the formula VIII ##STR11## in which R₂ and Xare as defined under formula I, by reaction with ammonia. Such reactionsare known and familiar to the expert.

The phenylsulfonyl chlorides of the formula VIII are novel compoundswhich have been developed and prepared specifically for the preparationof the active ingredients of the formula I. The present inventiontherefore likewise relates to them. The phenylsulfonyl chlorides of theformula VIII are prepared by reacting the correspondingly substituted2-chlorosulfonyl-benzoyl chlorides (cf., for example, D. Davis, Soc.2042, 2044 (1932)) with a compound of the formula IX ##STR12## in whichX is as defined under formula I, in the presence of a base. Suchreactions are known and familiar to the expert.

Phenylsulfonyl chlorides of the formula VIII in which X is oxygen canalso be prepared by reacting 2-isopropylthiobenzoic acid (of., forexample, H. Gilman, F. J. Webb, Am. Soc. 71, 4062-4063) with thionylchloride to give the corresponding benzoyl chloride, which is thenconverted into the corresponding oxetan-3-yl 2-isopropylthiobenzoatewith 3-hydroxyoxetane in the presence of a base, to give finally thesulfonylchloride of the formula VIII by reaction with chlorine. Suchreactions are known and familiar to the expert.

Compounds of the formula IX and their preparation are known (cf., forexample, B. Lamm et al., Acta Chem. Scand. 28,701 (1974) or J. Org.Chem. 48, 2953-2956 (1983)).

The sulfonylcarbamates and -thiocarbamates of the formula IV are noveland the present invention relates to them. They can be obtained, forexample, by reaction of the sulfonamides of the formula II with diphenylcarbamate or thiocarbamate in the presence of a base. Such reactions areknown and familiar to the expert.

The amines of the formula V are described in European PatentApplications 0 007 687, 0 030 138, 0 073 562 and 0 126 711, and in U.S.Pat. No. 4 579 584.

Processes for the preparation of N-pyfimidinyl- andN-triazinylcarbamates are described, for example, in EP-A-0 101 670.N-Triazolylcarbamates can be prepared analogously.

The active ingredients of the formula I are as a rule employedsuccessfully at rates of application of 0.001 to 2 kg/ha, in particular0.005 to 1 kg/ha. The doses required for the desired action can bedetermined by experiments. It depends on the nature of the action, thedevelopment stage of the crop plant and of the weed and on theapplication conditions (location, time, method) and can, as a result ofthese parameters, be varied within wide ranges.

The compounds of the formula I are distinguished by growth-inhibitingand herbicidal properties which render them excellent for use in cropsof useful plants, in particular in cereals, cotton, soya, rape, maizeand rice, use in soya crops and cereals being especially preferred.Control of the weeds in soya crops is preferably postemergence. Thecompounds of the formula I are distinguished in particular by their gooddegradability.

The invention also relates to herbicidal and plant growth-regulatingcompositions which comprise a novel active ingredient of the formula I,and methods for inhibition of plant growth.

Plant growth regulators are substances which cause agronomicallydesirable biochemical and/or physiological and/or morphological changesin/on the plants.

The active ingredients present in the compositions according to theinvention influence plant growth in various ways depending on the timeof application, dosage, mode of application and environmentalconditions. Plant growth regulators of the formula I can, for example,inhibit the vegetative growth of plants. This type of action is ofinterest on lawn areas, in the growing of ornamentals, in fruitplantations, on road embankments and on sports fields and industrialpremises, and also for controlled inhibition of secondary shoots, suchas on tobacco. In agriculture, inhibition of the vegetative growth ofcereals leads to reduced lodging via strengthening of the stem, andsimilar agronomic actions are achieved in rape, sunflowers, maize andother crop plants. The number of plants per unit area can moreover beincreased by inhibition of the vegetative growth. Another field of useof growth inhibitors is selective control of ground-covering plants inplantations or wide-row crops by severe inhibition of growth, withoutkilling these ground-covering plants, so that competition against themain crop is excluded, but the agronomically positive effects, such asprevention of erosion, nitrogen bonding and loosening of the soil, areretained.

A method for inhibition of plant growth is to be understood as meaningcontrol of the natural plant development without changing, in the senseof mutation, the life-cycle of the plants determined by geneticproperties. The method of growth regulation is used at a point in timeof the development of the plants which is to be determined in theindividual case. The active ingredients of the formula I can be appliedbefore or after emergence of the plants, for example even to the seedsor the seedlings, to roots, tubors, stems, leaves, flowers or otherplant parts. This can be effected, for example, by applying the activeingredient itself or in the form of a composition to the plants and/orby treatment of the nutrient medium of the plants (soil).

Various methods and techniques are suitable for use of the compounds ofthe formula I or compositions containing them for regulating plantgrowth, for example the following:

i) Seed dressing

a) Dressing the seeds with an active ingredient formulated as a wettablepowder by shaking in a vessel until the active ingredient is distributeduniformly over the seed surface (dry dressing). Up to 4 g of activeingredient of the formula I (in the case of a 50% formulation: up to 8.0g of wettable powder) are used here per kg of seed.

b) Dressing of the seeds with an emulsion concentrate of the activeingredient or with an aqueous solution of the active ingredient of theformula I formulated as a wettable powder by method a) (wet dressing).

c) Dressing by dipping the seed in a mixture containing up to 1000 ppmof active ingredient of the formula I for 1 to 72 hours and ifappropriate subsequent drying of the seed (seed soaking).

Dressing of the seed and treatment of the germinated seedling are ofcourse the preferred methods of application, because the treatment withthe active ingredient is directed completely toward the target crop. Asa rule 0.001 g to 4.0 g of active substance are used per kg of seed, itbeing possible to deviate upwards or downwards from the limitconcentrations stated (repeat dressing) depending on the method, whichalso allows the addition of other active ingredients or micronutrients.

ii) Controlled release of the active ingredient

The active ingredient is absorbed in solution onto mineral granulecarders or polymerised granules (urea/formaldehyde) and allowed to dry.If appropriate, a coating which allows the active ingredient to bereleased in metered form over a certain period of time can be applied(coated granules).

The compounds of the formula I are employed in unchanged form, asobtainable from the synthesis, or preferably with the auxiliariescustomary in formulation technology, and are therefore processed, forexample, to emulsifiable concentrates, directly sprayable or dilutablesolutions, dilute emulsions, wettable powders, soluble powders, dusts,granules and also capsules in, for example, polymeric substances in aknown manner. The methods of use, such as spraying, misting, dusting,wetting, sprinkling or pouring, are, like the nature of thecompositions, chosen according to the effects required and the givencircumstances.

The formulations, i.e. the compositions, formulations or preparationscomprising the active ingredient of the formula I and if appropriate oneor more solid or liquid additives, are prepared in a known manner, forexample by intimate mixing and/or grinding of the active ingredientswith extenders, for example with solvents, solid carriers and ifappropriate surface-active ingredients (surfactants).

Possible solvents are: aromatic hydrocarbons, in particular thefractions C₈ to C₁₂, such as mixtures of alkylbenzenes, for examplexylene mixtures, or alkylated naphthalenes; aliphatic and cycloaliphatichydrocarbons, such as paraffins, cyclohexane or tetrahydronaphthalene;alcohols, such as ethanol, propanol or butanol; glycols and ethers andesters thereof, such as propylene glycol or dipropylene glycol ether;ketones, such as cyclohexanone, isophorone or diacetone alcohol; strongpolar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide orwater; vegetable oils and esters thereof, such as rape, castor or soyaoil; and if appropriate also silicone oils.

Solid carders which are used, for example for dusts and dispersiblepowders, are as a rule natural rock powders, such as calcite, talc,kaolin, montmorillonite or attapulgite. Highly disperse silicic acid orhighly disperse absorbent polymers can also be added to improve thephysical properties. Granular, adsorbent granule carriers are poroustypes, for example pumice, crushed brick, sepiolite or bentonitc, andnon-sorbent carder materials are, for example, calcite or sand. A widerange of pregranulated materials of inorganic or organic nature, suchas, in particular, dolomite or comminuted plant residues, can moreoverbe used.

Surface-active ingredients are nonionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties,depending on the nature of the active ingredient of the formula I to beformulated. Surfactants is also to be understood as meaning surfactantmixtures.

Suitable anionic surfactants can be either so-called water-soluble soapsor water-soluble synthetic surface-active ingredients.

Soaps are the alkali metal, alkaline earth metal or substituted orunsubstituted ammonium salts of higher fatty acids (C₁₀ -C₂₂), forexample the sodium or potassium salts of oleic or stearic acid, or ofnaturally occurring fatty acid mixtures, which can be obtained, forexample, from coconut oil or tallow oil. The fatty acid methyltaurinesalts may furthermore also be mentioned.

More often, however, so-called synthetic surfactants are used, inparticular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonatedbenzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or sulfates are as a rule in the form ofalkali metal, alkaline earth metal or substituted or unsubstitutedammonium salts and contain an alkyl radical having 8 to 22 C atoms,alkyl also including the alkyl moiety of acyl radicals, for example thesodium or calcium salt of ligninsulfonic acid, of dodecylsulfate or of afatty alcohol sulfate mixture prepared from naturally occurring fattyacids. These also include the salts of sulfuric acid esters and sulfonicacids of fatty alcohol-ethylene oxide adducts. The sulfonatedbenzimidazole derivatives preferably contain 2 sulfonic acid groups anda fatty acid radical having 8-22 C atoms. Alkylarylsulfonates are, forexample, the Na, Ca or triethanolamine salts of dodecylbenzenesulfonicacid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonicacid-formaldehyde condensation product.

Corresponding phosphates, for example salts of the phosphoric acid esterof a p-nonylphenol-(4-14)-ethylene oxide adduct, or phospholipids arefurthermore also suitable.

Nonionic surfactants are in particular polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, which can contain 3 to 30 glycol ether groupsand 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to18 carbon atoms in the alkyl radical of the alkylphenols.

Other suitable nonionic surfactants are the water-soluble polyethyleneoxide adducts, containing 20 to 250 ethylene glycol ether groups and 10to 100 propylene glycol ether groups, with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usuallycontain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants are nonylphenol polyethoxyethanols,castor oil polyglycol ether, polypropylene-polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylenesorbitan, such aspolyoxyethylenesorbitan trioleate, are furthermore also suitable.

The cationic surfactants are in particular quaternary ammonium saltswhich contain at least one alkyl radical having 8 to 22 C atoms as theN-substituent and lower halogenated or unhalogenated alkyl, benzyl orlower hydroxyalkyl radicals as further substituents. The salts arepreferably in the form of halides, methylsulfates or ethylsulfates, forexample stearyltrimethylammonium chloride orbenzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customary in formulation technology are described, interalia, in the following publications:

"McCutcheon's Detergents and Emulsifiers Annual", Mc Publishing Corp.,Glen Rock, N.J., 1988.

M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, ChemicalPublishing Co., New York, 1980-1981.

Dr. Helmut Stache "Tensid-Taschenbuch"(Surfactant Handbook), CarlerHanser Verlag, Munich/Vienna 1981.

The pesticidal compositions as a rule comprise 0.1 to 99%, in particular0.1 to 95%, of active ingredient of the formula I, 1 to 99% of a solidor liquid additive and 0 to 25%, in particular 0.1 to 25%, of asurfactant.

While concentrated compositions are more preferable as commercial goods,the end user as a rule uses dilute compositions.

The compositions can also contain other additives, such as stabilisers,for example epoxidised or unepoxidised vegetable oils (epoxidisedcoconut oil, rape oil or soya oil), foam suppressants, for examplesilicone oil, preservatives, viscosity regulators, binders, tackifiersand fertilisers, or other active ingredients to achieve specificeffects.

Preferred formulations have, in particular, the following composition:(%=per cent by weight)

    ______________________________________                                        Emulsifiable concentrates:                                                    Active ingredient:                                                                           1 to 20%, preferably 5 to 10%                                  Surface-active agent:                                                                        5 to 30%, preferably 10 to 20%                                 Liquid carrier:                                                                              15 to 94%, preferably 70 to 85%                                Dusts:                                                                        Active ingredient:                                                                           0.1 to 10%, preferably 0.1 to 1%                               Solid carrier: 99.9 to 90%, preferably 99.9 to 99%                            Suspension concentrates:                                                      Active ingredient:                                                                           5 to 75%, preferably 10 to 50%                                 Water:         94 to 24%, preferably 88 to 30%                                Surface-active agent:                                                                        1 to 40%, preferably 2 to 30%                                  Wettable powders:                                                             Active ingredient:                                                                           0.5 to 90%, preferably 1 to 80%                                Surface-active agent:                                                                        0.5 to 20%, preferably 1 to 15%                                Solid carrier: 5 to 95%, preferably 15 to 90%                                 Granules:                                                                     Active ingredient:                                                                           0.5 to 30%, preferably 3 to 15%                                Solid carrier: 99.5 to 70%, preferably 97 to 85%                              ______________________________________                                    

PREPARATION EXAMPLES EXAMPLE H1 2-(Thiaetan-3-oxycarbonyl)phenylsulfonylchloride ##STR13##

A solution of 52.8 g of 2-chlorosulfonylbenzoyl chloride and 100 ml ofabsolute toluene is added dropwise to a mixture of 20.7 g of3-hydroxythiaetan, 20.0 g of pyridine and 250 ml of absolute toluene ata temperature of 0° to 10° C. The reaction mixture is then stirred at atemperature of 20°-25° C. for 2 hours and 300 ml of ice-water aresubsequently added. A toluene solution of2-thiaetanoxycarbonylphenylsulfonyl chloride is obtained by separatingoff the organic phase, washing it with water and drying it over sodiumsulfate, and is employed in Example H2 without further working up.

EXAMPLE H2 2-(Thiaetan-3-oxycarbonyl)phenylsulfonamide ##STR14##

8.5 g of ammonia are passed into a toluene solution of2-(thiaetan-3-oxycarbonyl)phenylsulfonyl chloride (preparation describedin Example H1) in the course of 1 hour. After 400 ml of ice-water hasbeen added to the reaction mixture, the mixture has been filtered andthe product has been washed with water and then dried, 39.3 g of2-thiaetanoxycarbonylphenylsulfonamide having a melting point of 145 to146° C. are obtained.

EXAMPLE H3N-[2-(Thiaetan-3-oxycarbonyl)phenylsulfonyl]-N'-(4-chloro-6-methoxy-1,3-pyrimidin- 2-yl)urea ##STR15##

A mixture of 0.69 g of diazabicyclo-[5.4.0]-undec-7-ene (1.5-5) and 5 mlof absolute dioxane is added dropwise to a mixture of 1.23 g of2-(thiaetan-3-oxycarbonyl)phenylsulfonamide, 1.26 g of4-chloro-6-methoxy-1,3-pyrimidin-2-yl phenylcarbamate and 20 ml ofabsolute dioxane and the mixture is then stirred at a temperature of20°to 25° C. for 4 hours. Pouring the mixture into water, dropwiseaddition of 10% hydrochloric acid to pH 5, extraction with ethylacetate, drying of the organic phase, evaporation and crystallisationfrom ethyl acetate gives 1.15 g ofN-[2-(thiaetan-3-oxycarbonyl)phenylsulfonyl]-N'-(4-chloro-6-methoxy-1,3-pyrimidin-2-yl)urea of melting point 180°to 181° C. (decomposition).

EXAMPLE H4 2-Isopropylthiobenzoyl chloride ##STR16##

A mixture of 15.7 g of 2-isopropylthiobenzoic acid and 15.7 g of thionylchloride is heated to the reflux temperature very slowly and kept underreflux until the evolution of gas has ended. 17.3 g of non-purified2-isopropylsulfonylbenzoyl chloride are obtained as a yellow oil byevaporating off all the excess thionyl chloride.

EXAMPLE H5 Oxetan-3-yl 2-isopropylthiobenzoate ##STR17##

A mixture of 12.9 g of 2-isopropylthiobenzoyl chloride and 20 ml ofabsolute toluene is added dropwise to a mixture of 4.44 g of3-hydroxyoxetane, 6.64 g of pyridine and 60 ml of absolute toluene at atemperature of 15°to 20° C. The suspension formed is stirred at atemperature of 20°-25° C. for 2 hours and at a temperature of 40°-45° C.for a further 3 hours. Adding water to the reaction mixture, washing theorganic phase with water and drying and evaporating it gives 12.6 g ofoxetan-3-yl 2-isopropylthiobenzoate as a pale yellow oil.

EXAMPLE H6 2-(Oxetan-3-oxycarbonyl)phenylsulfonyl chloride ##STR18##

11.2 g of chlorine are passed into a mixture of 12.6 g of oxetan-3-yl2-isopropylthiobenzoate, 12.9 g of sodium acetate and 100 ml of 50%acetic acid at a temperature of -5° to 0° C. in the course of 1 hour,and the mixture is then stirred at a temperature of 0° C. for 15minutes. By adding methylene chloride to the reaction mixture, washingthe organic phase with ice-water and drying it, a methylene chloridesolution of 2-(oxetan-3-oxycarbonyl)-phenylsulfonyl chloride isobtained, which is employed in Example H7 without further purification.

EXAMPLE H7 2-(Oxetan-3-oxycarbonyl)phenylsulfonarnide ##STR19##

2.5 g of ammonia are passed into a methylene chloride solution of2-(oxetan-3-oxycarbonyl)phenylsulfonyl chloride (Example H6) at atemperature of 0° to 5° C. in the course of 45 minutes. By adding waterto the reaction mixture, washing the organic phase with water, dryingand evaporating it and crystallising the residue from a methylenechloride/diethyl ether mixture, 6.7 g of2-(oxetan-3-oxycarbonyl)phenylsulfonamide of melting point 169° to 170°C. are obtained.

EXAMPLE H8N,[2-(Oxetan-3-oxycarbonyl)phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazinyl)-urea(compound No. 3.011 ) ##STR20##

A mixture of 1.52 g of diazabicyclo-[5.4.0]-undec-7-ene(1.5-5) and 5 mlof absolute dioxane is added dropwise to a mixture of 2.57 g of2-(oxetan-3-oxycarbonyl)phenylsulfonamide, 2.6 g of4-methoxy-6-methyl-1,3,5-triazinyl phenylcarbamate and 40 ml of absolutedioxane at 20°-25° C., and the mixture is then stirred at a temperatureof 20° to 25° C for 4 hours. By adding to water, dropwise addition of10% hydrochloric acid to establish a pH of 5, extraction with ethylacetate, drying of the organic phase, evaporation and crystallisationfrom ethyl acetate, 2.8 g ofN-[2-(oxetan-3-oxycarbonyl)phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazinyl)urea (compound No. 3.011) of melting point 162° to 163°C. (decomposition) are obtained.

EXAMPLE H9 Phenyl N-[2-(oxetan-3-oxycarbonyl)phenylsulfonyl]carbamate(compound No. 1.030) ##STR21##

A mixture of 2.57 g of 2-(oxetan-3-oxycarbonyl)phenylsulfonamide, 2.14 gof diphenyl carbonate, 1.38 g of potassium carbonate and 13 ml ofdimethylformamide is stirred at a temperature of 20°-25° C. for 15hours. The reaction mixture is then poured into ice-water, the pH isbrought to a value of 5-6 by dropwise addition of 10% hydrochloric acidand the mixture is extracted with ethyl acetate and washed with water.After drying over sodium sulfate, evaporation and crystallisation of theresidue from diethyl ether, 2.2 g of phenylN-[2-(oxetan-3-oxycarbonyl)phenylsulfonyl)carbamate (compound 1.030) ofmelting point 91°-92° C. are obtained.

EXAMPLE H10N-[2-(oxetan-3-oxycarbonl)phenylsulfonyl]-N'-[4-methoxy-6-(2,2,2-trifluoroethoxy)-pyrimidin-2-yl]urea(compound No. 2.034) ##STR22##

A mixture of 0.75 g of phenylN-[2-(oxetan-3-oxycarbonyl)phenylsulfonyl]carbamate, 0.34 g of2-amino-4-methoxy-6-(2,2,2-trifluoroethoxy)pyrimidine and 7 ml ofdioxane is stirred at a temperature of 90°-95° C. for 4 hours. After thereaction mixture has been evaporated and the residue crystallised fromacetone, 0.7 g ofN-[2-(oxetan-3-oxycarbonyl)phenylsulfonyl]-N'-[4-methoxy-6-(2,2,2-trifluoroethoxy)-pyrimidin-2-yl]urea(compound No. 2.034) of melting point 185°-186° C. is obtained.

The compounds of the formula I listed in the attached tables andintermediates thereof are prepared in an analogous manner.

                                      TABLE 1                                     __________________________________________________________________________    Intermediates of the formula                                                   ##STR23##                                                                    Compound                            Melting                                   No.   R.sub.2   L                X  point [°C.]                        __________________________________________________________________________    1.001 H         Cl               O  oil                                       1.002 H         Cl               S  oil                                       1.003 H         NH.sub.2         O  169-170°                           1.004 H         NH.sub.2         S  145-146°                           1.005 H         NH.sub.2         SO                                           1.006 H         NH.sub.2         SO.sub.2                                                                         213-214°                           1.007 5-F       NH.sub.2         O                                            1.008 5-F       NH.sub.2         S                                            1.009 5-CF.sub.3                                                                              NH.sub.2         O                                            1.010 5-Cl      NH.sub.2         O                                            1.011 5-OCH.sub.3                                                                             NH.sub.2         O                                            1.012 5-CH.sub.2 CH.sub.2 CF.sub.3                                                            NH.sub.2         O                                            1.013 5-OCH.sub.2 CH.sub.2 Cl                                                                 NH.sub.2         O                                            1.014 5-OCHF.sub.2                                                                            NH.sub.2         O                                            1.015 5-OCH.sub.2 CH.sub.2 OCH.sub.3                                                          NH.sub.2         O                                            1.016 5-CH.sub.3                                                                              NH.sub.2         O                                            1.017 5-OCH.sub.2 CHCH.sub.2                                                                  NH.sub.2         O                                            1.018 6-Cl      NH.sub.2         O                                            1.019 6-F       NH.sub.2         O                                            1.020 3-Cl      NH.sub.2         O                                            1.021 3-F       NH.sub.2         O                                            1.022 5-NO.sub.2                                                                              NH.sub.2         O                                            1.023 5-CCH     NH.sub.2         O                                            1.024 5-CHCHCF.sub.3                                                                          NH.sub.2         O                                            1.025 5-CH.sub.2CCH                                                                           NH.sub.2         O                                            1.026 5-CN      NH.sub.2         O                                            1.027 5-N(CH.sub.3).sub.2                                                                     NH.sub.2         O                                            1.028 5-SCH.sub.2 CHF.sub.2                                                                   NH.sub.2         O                                            1.029 H                                                                                        ##STR24##       O                                            1.030 H                                                                                        ##STR25##       O  91-92°                             1.031 5-F                                                                                      ##STR26##       O                                            1.032 4-F                                                                                      ##STR27##       O                                            1.033 4-F       Cl               O                                            1.034 4-F       NH.sub.2         O                                            1.035 4-OCH.sub.3                                                                             Cl               O                                            1.036 4-OCH.sub.3                                                                             NH.sub.2         O                                            1.037 4-OCH.sub.3                                                                              ##STR28##       O                                            1.038 5-OCH.sub.3                                                                             NH.sub.2         O                                            1.039 5-OCH.sub.3                                                                              ##STR29##       O                                            1.040 6-CH.sub.3                                                                              NH.sub.2         O                                            1.041 6-Cl                                                                                     ##STR30##       O                                            1.042 5-CCH.sub.3                                                                              ##STR31##       O                                            1.043 5-CHCCH.sub.3                                                                           NH.sub.2         O                                            __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    Compounds of the formula Ia                                                    ##STR32##                                                                    Comp. No.                                                                           R.sub.1                                                                          R.sub.2   R.sub.8                                                                             R.sub.9  X  m.p. [°C.]                        __________________________________________________________________________    2.001 H  H         CH.sub.3                                                                            CH.sub.3 O  161-162°                          2.002 H  H         CH.sub.3                                                                            OCH.sub.3                                                                              O  153-155°                                                               (decomposition)                          2.003 H  H         OCH.sub.3                                                                           OCH.sub.3                                                                              O  166-167°                          2.004 H  H         OCH.sub.3                                                                           OCHF.sub.2                                                                             O  181-183°                          2.005 H  H         CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                       O                                           2.006 H  H         OCH.sub.3                                                                           OC.sub.2 H.sub.5                                                                       O                                           2.007 H  H         CH.sub.3                                                                            OCHF.sub.2                                                                             O  165-167°                          2.008 H  H         OCHF.sub. 2                                                                         OCHF.sub.2                                                                             O  164-166°                          2.009 H  H         OCH.sub.3                                                                            ##STR33##                                                                             O                                           2.010 H  H         OC.sub.2 H.sub.5                                                                    OCHF.sub.2                                                                             O                                           2.011 H  H         CH.sub.3                                                                            SCHF.sub.2                                                                             O                                           2.012 H  H         Cl    OCH.sub.3                                                                              O  175-177°                                                               (decomposition)                          2.013 H  H         Cl    OCHF.sub.2                                                                             O                                           2.014 H  H         Cl    SCHF.sub.2                                                                             O                                           2.015 H  H         CH.sub.2 Cl                                                                         CH.sub.3 O                                           2.016 H  H         CH.sub.2 Cl                                                                         OCH.sub.3                                                                              O                                           2.017 H  H         CH.sub.2 OCH.sub.3                                                                  OCH.sub.3                                                                              O                                           2.018 H  H         CH.sub.3                                                                            SCH.sub.3                                                                              O                                           2.019 H  H         OCH.sub.3                                                                           SCH.sub.3                                                                              O                                           2.020 H  H         Cl    SCH.sub.3                                                                              O                                           2.021 H  H         HNCH.sub.3                                                                          CH.sub.3 O                                           2.022 H  H         HNCH.sub.3                                                                          OCH.sub.3                                                                              O                                           2.023 H  H         HNCH.sub.3                                                                          OC.sub.2 H.sub.5                                                                       O                                           2.024 H  H         N(CH.sub.3).sub.2                                                                   CH.sub.3 O                                           2.025 H  H         N(CH.sub.3).sub.2                                                                   OCH.sub.3                                                                              O                                           2.026 H  H         OC.sub.2 H.sub.5                                                                    OCH.sub.3                                                                              O                                           2.027 H  H         OC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                        O                                           2.028 H  H         N(CH.sub.3).sub.2                                                                   OCHF.sub.2                                                                             O                                           2.029 H  H         CH.sub.2 SCH.sub.3                                                                  OCH.sub.3                                                                              O                                           2.030 H  H         CH.sub.2 F                                                                          OCH.sub.3                                                                              O                                           2.031 H  H         F     OCH.sub.3                                                                              O                                           2.032 H  H         OC.sub.2 H.sub.5                                                                    OC.sub.2 H.sub.5                                                                       O                                           2.033 H  H         CH.sub.3                                                                            OCH.sub.2 CF.sub.3                                                                     O                                           2.034 H  H         OCH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                     O  185-186°                          2.035 H  H         N(CH.sub.3).sub.2                                                                   OCH.sub.2 CF.sub.3                                                                     O                                           2.036 H  H         OCH.sub.3                                                                           OC.sub.3 H.sub.7 (i)                                                                   O                                           2.037 H  H         CF.sub.3                                                                            CH.sub.3 O                                           2.038 H  H         CF.sub.3                                                                            OCH.sub.3                                                                              O                                           2.039 H  H         CF.sub.3                                                                            OC.sub.2 H.sub.5                                                                       O                                           2.040 H  H         Cl    CH.sub.3 O                                           2.041 H  H         Cl    CF.sub.3 O                                           2.042 H  H         Cl    OCH.sub.2 CF.sub.3                                                                     O                                           2.043 CH.sub.3                                                                         H         CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.044 CH.sub.3                                                                         H         Cl    OCH.sub.3                                                                              O                                           2.045 CH.sub.3                                                                         H         OCH.sub.3                                                                           OCH.sub.3                                                                              O                                           2.046 CH.sub.3                                                                         H         CH.sub.3                                                                            CH.sub.3 O                                           2.047 H  5-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.048 H  5-F       CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.049 H  6-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.050 H  6-F       CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.051 H  5-CF.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.052 H  5-OCH.sub.3                                                                             CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.053 H  5-NO.sub.2                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.054 H  3-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.055 H  3-F       CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.056 H  5-CCH     CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.057 H  5-CHCHCF.sub.3                                                                          CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.058 H  5-CH.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.059 H  5-OCH.sub.2 CH.sub.2 Cl                                                                 CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.060 H  5-OCHF.sub.2                                                                            CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.061 H  5-OCH.sub.2 CHCH.sub.2                                                                  CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.062 H  5-OCH.sub.2 CCH                                                                         CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.063 H  5-CN      CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.064 H  5-N(CH.sub.3).sub.2                                                                     CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.065 H  5-CH.sub.2 CH.sub.2 CF.sub.3                                                            CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.066 H  5-OCH.sub.2 CH.sub.2 OCH.sub.3                                                          CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.067 H  5-SCH.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.068 H  H         OC.sub.2 H.sub. 5                                                                    ##STR34##                                                                             O                                           2.069 H  H         C.sub.3 H.sub.7 (i)                                                                 OCH.sub.3                                                                              O                                           2.070 H  H         NH.sub.2                                                                            OCH.sub.3                                                                              O                                           2.071 H  H         OCH.sub.3                                                                           SCH.sub.2 CF.sub.3                                                                     O                                           2.072 H  H         OCH.sub.3                                                                           OCH.sub.2 CH.sub.3 OCH.sub.3                                                           O                                           2.073 H  H         F     OCHF.sub.2                                                                             O                                           2.074 H  5-Cl      Cl    OCH.sub.3                                                                              O                                           2.075 H  5-F       Cl    OCH.sub.3                                                                              O                                           2.076 H  5-CF.sub.3                                                                              Cl    OCH.sub.3                                                                              O                                           2.077 H  5-CH.sub.3                                                                              Cl    OCH.sub.3                                                                              O                                           2.078 H  5-OCH.sub.3                                                                             Cl    OCH.sub.3                                                                              O                                           2.079 H  5-F       CH.sub.3                                                                            CH.sub.3 O                                           2.080 H  5-F       OCH.sub.3                                                                           OCH.sub.3                                                                              O                                           2.081 H  5-OCHF.sub.2                                                                            Cl    OCH.sub.3                                                                              O                                           2.082 H  H         CH.sub.3                                                                            CH.sub.3 S  172-174°                                                               (decomposition)                          2.083 H  H         CH.sub.3                                                                            OCH.sub.3                                                                              S  176-177°                                                               (decomposition)                          2.084 H  H         OCH.sub.3                                                                           OCH.sub.3                                                                              S  187-188°                                                               (decomposition)                          2.085 H  H         OCH.sub.3                                                                           OCHF.sub.2                                                                             S                                           2.086 H  H         CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                       S                                           2.087 H  H         OCH.sub.3                                                                           OC.sub.2 H.sub.5                                                                       S                                           2.088 H  H         CH.sub.3                                                                            OCHF.sub.2                                                                             S                                           2.089 H  H         OCHF.sub.2                                                                          OCHF.sub.2                                                                             S                                           2.090 H  H         OCH.sub.3                                                                            ##STR35##                                                                             S                                           2.091 H  H         OC.sub.2 H.sub.5                                                                    OCHF.sub.2                                                                             S                                           2.092 H  H         CH.sub.3                                                                            SCHF.sub.2                                                                             S                                           2.093 H  H         Cl    OCH.sub.3                                                                              S  180-181°                                                               (decomposition)                          2.094 H  H         Cl    OCHF.sub.2                                                                             S                                           2.095 H  H         Cl    SCHF.sub.2                                                                             S                                           2.096 H  H         CH.sub.2 Cl                                                                         CH.sub.3 S                                           2.097 H  H         CH.sub.2 Cl                                                                         OCH.sub.3                                                                              S                                           2.098 H  H         CH.sub.2 OCH.sub.3                                                                  OCH.sub.3                                                                              S                                           2.099 H  H         CH.sub.3                                                                            SCH.sub.3                                                                              S                                           2.100 H  H         OCH.sub.3                                                                           SCH.sub.3                                                                              S                                           2.101 H  H         Cl    SCH.sub.3                                                                              S                                           2.102 H  H         HNCH.sub.3                                                                          CH.sub.3 S                                           2.103 H  H         HNCH.sub.3                                                                          OCH.sub.3                                                                              S                                           2.104 H  H         HNCH.sub.3                                                                          OC.sub.2 H.sub.5                                                                       S                                           2.105 H  H         N(CH.sub.3).sub.2                                                                   CH.sub.3 S                                           2.106 H  H         N(CH.sub.3).sub.2                                                                   OCH.sub.3                                                                              S                                           2.107 H  H         C.sub.2 H.sub.5                                                                     OCH.sub.3                                                                              S                                           2.108 H  H         C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                       S                                           2.109 H  H         N(CH.sub.3).sub.2                                                                   OCHF.sub.2                                                                             S                                           2.110 H  H         CH.sub.2 SCH.sub.3                                                                  OCH.sub.3                                                                              S                                           2.111 H  H         CH.sub.2 F                                                                          OCH.sub.3                                                                              S                                           2.112 H  H         F     OCH.sub.3                                                                              S                                           2.113 H  H         OC.sub.2 H.sub.5                                                                    OC.sub.2 H.sub.5                                                                       S                                           2.114 H  H         CH.sub.3                                                                            OCH.sub.2 CF.sub.3                                                                     S                                           2.115 H  H         OCH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                     S                                           2.116 H  H         N(CH.sub.3).sub.2                                                                   OCH.sub.2 CF.sub.3                                                                     S                                           2.117 H  H         OCH.sub.3                                                                           OC.sub.3 H.sub.7 (i)                                                                   S                                           2.118 H  H         CF.sub.3                                                                            CH.sub.3 S                                           2.119 H  H         CF.sub.3                                                                            OC.sub.2 H.sub.5                                                                       S                                           2.120 H  H         Cl    CH.sub.3 S                                           2.121 H  H         Cl    CF.sub.3 S                                           2.112 H  H         Cl    OCH.sub.2 CF.sub.3                                                                     S                                           2.123 CH.sub.3                                                                         H         CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.124 CH.sub.3                                                                         H         Cl    OCH.sub.3                                                                              S                                           2.125 CH.sub.3                                                                         H         OCH.sub.3                                                                           OCH.sub.3                                                                              S                                           2.126 CH.sub.3                                                                         H         CH.sub.3                                                                            CH.sub.3 S                                           2.127 H  5-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.128 H  5-F       CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.129 H  6-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.130 H  6-F       CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.131 H  5-CF.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.132 H  5-OCH.sub.3                                                                             CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.133 H  5-NO.sub.2                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.134 H  H         CF.sub.3                                                                            OCH.sub.3                                                                              S                                           2.135 H  H         CH.sub.3                                                                            CH.sub.3 SO                                          2.136 H  H         CH.sub.3                                                                            OCH.sub.3                                                                              SO                                          2.137 H  H         Cl    OCH.sub.3                                                                              SO                                          2.138 H  H         OCH.sub.3                                                                           OCH.sub.3                                                                              SO                                          2.139 H  H         CH.sub.3                                                                            CH.sub.3 SO.sub.2                                    2.140 H  H         CH.sub.3                                                                            OCH.sub.3                                                                              SO.sub.2                                    2.141 H  H         Cl    OCH.sub.3                                                                              SO.sub.2                                    2.142 H  H         OCH.sub.3                                                                           OCH.sub.3                                                                              SO.sub.2                                                                         160-161°                                                               (decomposition)                          2.143 H  H         OC.sub.2 H.sub.5                                                                     ##STR36##                                                                             S                                           2.144 H  H         C.sub.3 H.sub.7                                                                     OCH.sub.3                                                                              S                                           2.145 H  H         NH.sub.2                                                                            OCH.sub.3                                                                              S                                           2.146 H  H         OCH.sub.3                                                                           SCH.sub.2 CF.sub.3                                                                     S                                           2.147 H  H         OCH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                                                           S                                           2.148 H  H         F     OCHF.sub.2                                                                             S                                           2.149 H  3-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.150 H  3-Cl      Cl    OCH.sub.3                                                                              S                                           2.151 H  3-F       CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.152 H  3-F       Cl    OCH.sub. 3                                                                             S                                           2.153 H  5-CCH     CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.154 H  5-CHCHCF.sub.3                                                                          CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.155 H  5-CH.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.156 H  5-OCH.sub.2 CH.sub.2 Cl                                                                 CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.157 H  5-OCHF.sub.2                                                                            CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.158 H  5-OCH.sub.2 CHCH.sub.2                                                                  CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.159 H  5-OCH.sub.2 CCH                                                                         CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.160 H  5-CH.sub.2 CH.sub.2 CF.sub.3                                                            CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.161 H  5-OCH.sub.2 CH.sub.2 OCH.sub.3                                                          CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.162 H  5-SCH.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                            OCH.sub.3                                                                              S                                           2.163 H  6-CH.sub.3                                                                              N(CH.sub.3).sub.2                                                                   OCH.sub.2 CF.sub.3                                                                     O                                           2.164 H  5-OCH.sub.2 CH.sub.2 Cl                                                                 CH.sub.3                                                                            CH.sub.3 O                                           2.165 H  5-OCH.sub.2 CH.sub.2 Cl                                                                 OCH.sub.3                                                                           OCH.sub.3                                                                              O                                           2.166 H  5-CCCH.sub.3                                                                            OCH.sub.3                                                                           OCH.sub.3                                                                              O                                           2.167 H  5-C CCH.sub.3                                                                           OCH.sub.3                                                                           CH.sub.3 O                                           2.168 H  5-CCCH.sub.3                                                                            CH.sub.3                                                                            CH.sub.3 O                                           2.169 H  4-F       CH.sub.3                                                                            CH.sub.3 O                                           2.170 H  4-F       OCH.sub.3                                                                           CH.sub.3 O                                           2.171 H  4-OCH.sub.3                                                                             OCH.sub.3                                                                           CH.sub.3 O                                           2.172 H  4-OCH.sub.3                                                                             CH.sub.3                                                                            Ch.sub.3 O                                           2.173 H  5-CCH     CH.sub.3                                                                            CH.sub.3 O                                           2.174 H  5-CCH     OCH.sub.3                                                                           CH.sub.3 O                                           2.175 H  5-CCH     OCH.sub.3                                                                           OCH.sub.3                                                                              O                                           2.176 H  6-CH.sub.2 F                                                                            OCH.sub.3                                                                           OCH.sub.3                                                                              O                                           2.177 H  6-CH.sub.2 F                                                                            CH.sub.3                                                                            CH.sub.3 O                                           2.178 H  6-CH.sub.2 F                                                                            CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.179 H  5-CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                            OCH.sub.3                                                                              O                                           2.180 H  5-CH.sub.2 CH.sub.3                                                                     CH.sub.3                                                                            CH.sub.3 O                                           __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    Compounds of the formula Ib:                                                   ##STR37##                                                                    Comp. No.                                                                           R.sub.1                                                                          R.sub.2   R.sub.8                                                                             R.sub.9  X  m.p. [°C.]                        __________________________________________________________________________    3.001 H  H         CH.sub.3                                                                            CH.sub.3 O                                           3.002 H  H         CH.sub.3                                                                            SCH.sub.3                                                                              O                                           3.003 H  H         OCH.sub.3                                                                           OCH.sub.3                                                                              O  185-187°                                                               (decomposition)                          3.004 H  H         CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                       O  158-160°                          3.005 H  H         OCH.sub.3                                                                           OC.sub.2 H.sub.5                                                                       O                                           3.006 H  H         OCH.sub.3                                                                            ##STR38##                                                                             O  154-156°                          3.007 H  H         CH.sub.2 Cl                                                                         OCH.sub.3                                                                              O                                           3.008 H  H         CH.sub.2 OCH.sub.3                                                                  OCH.sub.3                                                                              O                                           3.009 H  H         CH.sub.2 SCH.sub.3                                                                  OCH.sub.3                                                                              O                                           3.010 H  H         OC.sub.2 H.sub.5                                                                    OC.sub.2 H.sub.5                                                                       O                                           3.011 H  H         CH.sub.3                                                                            OCH.sub.3                                                                              O  162-163°                                                               (decomposition)                          3.012 H  H         OCH.sub.3                                                                           SCH.sub.3                                                                              O                                           3.013 H  H         OCH.sub.3                                                                           OC.sub.3 H.sub.7 (i)                                                                   O                                           3.014 H  H         HNCH.sub.3                                                                          CH.sub.3 O                                           3.015 H  H         HNCH.sub.3                                                                          OCH.sub.3                                                                              O                                           3.016 H  H         HNCH.sub.3                                                                          OC.sub.2 H.sub.5                                                                       O                                           3.017 H  H         N(CH.sub.3).sub.2                                                                   CH.sub.3 O                                           3.018 H  H         N(CH.sub.3).sub.2                                                                   OCH.sub.3                                                                              O  169-170°                                                               (decomposition)                          3.019 H  H         C.sub.2 H.sub.5                                                                     OCH.sub.3                                                                              O  169-171°                                                               (decomposition)                          3.020 H  H         CH.sub.2 F                                                                          OCH.sub.3                                                                              O                                           3.021 H  H         CH.sub.3                                                                            OCH.sub.2 CF.sub.3                                                                     O                                           3.022 H  H         OCH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                     O  180-182°                          3.023 H  H         N(CH.sub.3).sub.2                                                                   OCH.sub.2 CF.sub.3                                                                     O  177-178°                          3.024 H  H         CF.sub.3                                                                            OCH.sub.3                                                                              O                                           3.025 H  H         OCH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                                                           O                                           3.026 CH.sub.3                                                                         H         CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.027 CH.sub.3                                                                         H         OCH.sub.3                                                                           OCH.sub.3                                                                              O                                           3.028 H  5-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.029 H  5-F       CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.030 H  6-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.031 H  6-F       CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.032 H  5-CF.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.033 H  5-OCH.sub.3                                                                             CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.034 H  5-NO.sub.2                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.035 H  5-CCH     CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.036 H  5-CHCHCF.sub.3                                                                          CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.037 H  5-CH.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.038 H  5-OCH.sub.2 CH.sub.2 Cl                                                                 CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.039 H  5-OCHF.sub.2                                                                            CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.040 H  3-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.041 H  3-F       CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.042 H  H         OC.sub.2 H.sub.5                                                                     ##STR39##                                                                             O  152-153°                          3.043 H  H         C.sub.3 H.sub.7 (i)                                                                 OCH.sub.3                                                                              O                                           3.044 H  H         OCH.sub.3                                                                           SCH.sub.2 CF.sub.3                                                                     O                                           3.045 H  H         NH.sub.2                                                                            OCH.sub.3                                                                              O                                           3.046 H  5-OCH.sub.2 CHCH.sub.2                                                                  CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.047 H  5-OCH.sub.2 CCH                                                                         CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.048 H  5-CN      CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.049 H  5-N(CH.sub.3).sub.2                                                                     CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.050 H  5-CH.sub.2CH.sub.2CF.sub.3                                                              CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.051 H  5-OCH.sub.2 CH.sub.2 OCH.sub.3                                                          CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.052 H  5-SCH.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                            OCH.sub.3                                                                              O                                           3.053 H  H         CH.sub.3                                                                            OCH.sub.3                                                                              S  164-165°                                                               (decomposition)                          3.054 H  H         CH.sub.3                                                                            CH.sub.3 S                                           3.055 H  H         OCH.sub.3                                                                           OCH.sub.3                                                                              S                                           3.056 H  H         CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                       S                                           3.057 H  H         OCH.sub.3                                                                           OC.sub.2 H.sub.5                                                                       S                                           3.058 H  H         OCH.sub.3                                                                            ##STR40##                                                                             S                                           3.059 H  H         CH.sub.2 Cl                                                                         OCH.sub.3                                                                              S                                           3.060 H  H         CH.sub.2 OCH.sub.3                                                                  OCH.sub.3                                                                              S                                           3.061 H  H         CH.sub.2 SCH.sub.3                                                                  OCH.sub.3                                                                              S                                           3.062 H  H         OC.sub.2 H.sub.5                                                                    OC.sub.2 H.sub.5                                                                       S                                           3.063 H  H         CH.sub.3                                                                            SCH.sub.3                                                                              S                                           3.064 H  H         OCH.sub.3                                                                           SCH.sub.3                                                                              S                                           3.065 H  H         OCH.sub.3                                                                           OC.sub.3 H.sub.7 (i)                                                                   S                                           3.066 H  H         HNCH.sub.3                                                                          CH.sub.3 S                                           3.067 H  H         HNCH.sub.3                                                                          OCH.sub.3                                                                              S                                           3.068 H  H         HNCH.sub.3                                                                          OC.sub.2 H.sub.5                                                                       S                                           3.069 H  H         N(CH.sub.3).sub.2                                                                   CH.sub.3 S                                           3.070 H  H         N(CH.sub.3).sub.2                                                                   OCH.sub.3                                                                              S                                           3.071 H  H         C.sub.2 H.sub.5                                                                     OCH.sub.3                                                                              S                                           3.072 H  H         CH.sub.2 F                                                                          OCH.sub.3                                                                              S                                           3.073 H  H         CH.sub.3                                                                            OCH.sub.2 CF.sub.3                                                                     S                                           3.074 H  H         OCH.sub.3                                                                           OCH.sub.2 CF.sub.3                                                                     S                                           3.075 H  H         N(CH.sub.3).sub.2                                                                   OCH.sub.2 CF.sub.3                                                                     S                                           3.076 H  H         CF.sub.3                                                                            OCH.sub.3                                                                              S                                           3.077 H  H         OCH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                                                           S                                           3.078 CH.sub.3                                                                         H         CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.079 CH.sub.3                                                                         H         OCH.sub.3                                                                           OCH.sub.3                                                                              S                                           3.080 H  5-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.081 H  5-F       CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.082 H  6-Cl      CH.sub. 3                                                                           OCH.sub.3                                                                              S                                           3.083 H  6-F       CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.084 H  5-CF.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.085 H  5-OCH.sub.3                                                                             CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.086 H  5-NO.sub.2                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.087 H  5-CCH     CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.088 H  5-CHCHCF.sub.3                                                                          CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.089 H  5-CH.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.090 H  5-OCH.sub.2 CH.sub.2 Cl                                                                 CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.091 H  5-OCHF.sub.2                                                                            CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.092 H  3-Cl      CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.093 H  3-F       CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.094 H  H         CH.sub.3                                                                            OCH.sub.3                                                                              SO                                          3.095 H  H         OCH.sub.3                                                                           OCH.sub.3                                                                              SO                                          3.096 H  H         CH.sub.3                                                                            OCH.sub.3                                                                              SO.sub.2                                    3.097 H  H         OCH.sub.3                                                                           OCH.sub.3                                                                              SO.sub.2                                    3.098 H  H         OC.sub.2 H.sub.5                                                                     ##STR41##                                                                             S                                           3.099 H  H         OC.sub.2 H.sub.5                                                                     ##STR42##                                                                             SO.sub.2                                    3.100 H  5-CH.sub.2CH.sub.2CF.sub.3                                                              CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.101 H  5-OCH.sub.2 CH.sub.2 OCH.sub.3                                                          CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.102 H  5-SCH.sub.2 CHF.sub.2                                                                   CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.103 H  5-OCH.sub.2 CHCH.sub.2                                                                  CH.sub.3                                                                            OCH.sub.3                                                                              S                                           3.104 H  H         C.sub.3 H.sub.7 (i)                                                                 OCH.sub.3                                                                              S                                           3.105 H  6-CH.sub.3                                                                              N(CH.sub.3).sub.2                                                                   OCH.sub.2 CF.sub.3                                                                     O                                           3.106 H  5-CCCH.sub.3                                                                            OCH.sub.3                                                                           CH.sub.3 O                                           3.107 H  H         OCH.sub.3                                                                           C.sub.2 H.sub.5                                                                        O                                           3.108 H  H         OC.sub.2 H.sub.5                                                                    OCH.sub.2 CH.sub.3                                                                     O                                           3.109 H  H         OCH.sub.3                                                                            ##STR43##                                                                             O                                           3.110 H  H         OC.sub.2 H.sub.5                                                                    N(CH.sub.3).sub.2                                                                      O                                           3.111 H  H         OCH.sub.3                                                                           OCH.sub.2 CH.sub.2 Cl                                                                  O                                           3.112 H  4-OCH.sub.3                                                                             OCH.sub.3                                                                           CH.sub.3 O                                           3.113 H  5-OCH.sub.2 CH.sub.2 Cl                                                                 OCH.sub.3                                                                           CH.sub.3 O                                           3.114 H  6-CH.sub.2 F                                                                            OCH.sub.3                                                                           CH.sub.3 O                                           3.115 H  5-CH.sub.2 CH.sub.3                                                                     OCH.sub.3                                                                           CH.sub.3 O                                           __________________________________________________________________________

                  TABLE 4                                                         ______________________________________                                        Compounds of the formula Ic:                                                   ##STR44##                                                                    Comp. No.                                                                             R.sub.2                                                                              R.sub.10 R.sub.11                                                                            R.sub.12                                                                             X    m.p. [°C.]                   ______________________________________                                        4.001   H      CH.sub.3 CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.002   H      CH.sub.3 OCH.sub.3                                                                           OCH.sub.3                                                                            O    185-187°                     4.003   H      CH.sub.3 OCH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     O                                        4.004   H      CH.sub.3 SCH.sub.3                                                                           OCH.sub.3                                                                            O                                        4.005   H      CH.sub.3 OC.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            O                                        4.006   H      CH.sub.3 Cl    OCH.sub.3                                                                            O                                        4.007   H      CH.sub.3 F     OCH.sub.3                                                                            O                                        4.008   H      Cl       CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.009   H      Cl       OCH.sub.3                                                                           OCH.sub.3                                                                            O    197-198°                     4.010   H      F        CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.011   H      CF.sub.3 CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.012   H      OCH.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.013   H      SCH.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.014   H      SOCH.sub.3                                                                             CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.015   H      SO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.016   H      CN       CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.017   H      OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.018   H      CH.sub.3 CH.sub.3                                                                            OCH.sub.3                                                                            S                                        4.019   H      CH.sub.3 OCH.sub.3                                                                           OCH.sub.3                                                                            S                                        4.020   H      Cl       CH.sub.3                                                                            OCH.sub.3                                                                            S                                        4.021   H      Cl       OCH.sub.3                                                                           OCH.sub.3                                                                            S                                        4.022   H      F        CH.sub.3                                                                            OCH.sub.3                                                                            S                                        4.023   H      H        OCH.sub.3                                                                           OCH.sub.3                                                                            S                                        4.024   H      H        OCH.sub.3                                                                           OCH.sub.3                                                                            O                                        4.025   H      CH.sub.3 OCH.sub.3                                                                           OCH.sub.3                                                                            SO                                       4.026   H      CH.sub.3 CH.sub.3                                                                            OCH.sub.3                                                                            SO.sub.2                                 4.027   H      CH.sub.3 OCH.sub.3                                                                           OCH.sub.3                                                                            SO.sub.2                                 4.028   H      Cl       OCH.sub.3                                                                           OCH.sub.3                                                                            SO.sub.2                                 4.029   5-F    CH.sub.3 CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.030   5-Cl   CH.sub.3 CH.sub.3                                                                            OCH.sub.3                                                                            O                                        4.031   H      CF.sub.3 CH.sub.3                                                                            OCH.sub.3                                                                            S                                        4.032   H      OCH.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                            S                                        ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Compounds of the formula Id:                                                   ##STR45##                                                                    Compound                               Melting                                No.      R.sub.2 R.sub.13                                                                              R.sub.14                                                                              X     point [°C.]                     ______________________________________                                        5.001    H       CH.sub.3                                                                              CH.sub.3                                                                              O                                            5.002    H       CH.sub.3                                                                              OCH.sub.3                                                                             O                                            5.003    H       CH.sub.3                                                                              Cl      O                                            5.004    H       CH.sub.3                                                                              OCHF.sub.2                                                                            O                                            5.005    H       C.sub.2 H.sub.5                                                                       OCH.sub.3                                                                             O                                            5.006    H       CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                      O                                            5.007    H       CH.sub.3                                                                              CH.sub.3                                                                              S                                            5.008    H       CH.sub.3                                                                              OCH.sub.3                                                                             S                                            5.009    H       CH.sub.3                                                                              Cl      S                                            5.011    H       CH.sub.3                                                                              CH.sub.3                                                                              SO                                           5.012    H       CH.sub.3                                                                              OCH.sub.3                                                                             SO                                           5.013    H       CH.sub.3                                                                              CH.sub.3                                                                              SO.sub.2                                     5.014    H       CH.sub.3                                                                              CH.sub.3                                                                              SO.sub.2                                     5.015    5-F     CH.sub.3                                                                              OCH.sub.3                                                                             O                                            5.016    5-Cl    CH.sub.3                                                                              OCH.sub.3                                                                             O                                            ______________________________________                                    

Formulation examples for active ingredients of the formula I (%=per centby weight)

    ______________________________________                                        1. Wettable powder    a)     b)      c)                                       ______________________________________                                        Active ingredient according to Tables 2-5                                                           20%    50%      0.5%                                    Sodium lignin sulfonate                                                                              5%     5%      5                                       Sodium lauryl sulfate  3%    --        --%                                    Sodium diisobutylnaphthalenesulfonate                                                               --      6%       6%                                     Octylphenol polyethylene glycol                                                                     --      2%       2%                                     ether (7-8 mol of ethylene oxide)                                             Highly disperse silicic acid                                                                         5%    27%       27%                                    Kaolin                67%    --%     --                                       Sodium chloride       --     --      59.5%                                    ______________________________________                                    

The active ingredient is mixed thoroughly with the additives and themixture is ground thoroughly in a suitable mill. Wettable powders whichcan be diluted with water to give suspensions of any desiredconcentration are obtained.

    ______________________________________                                        2. Emulsion concentrates                                                                              a)     b)                                             ______________________________________                                        active ingredient according to Tables 2-5                                                             10%    1%                                             Calcium dodecylbenzenesulfonate                                                                        3%    3%                                             Octylphenol polyethylene glycol                                                                        3%    3%                                             ether (4-5 mol of ethylene oxide)                                             Castor oil polyethylene glycol                                                                         4%    4                                              ether (36 mol of ethylene oxide)                                              Cyclohexanone           30     10%                                            Xylene mixture          50%    79%                                            ______________________________________                                    

Emulsions of any desired concentation can be prepared from suchconcentrates by dilution with water.

    ______________________________________                                        3. Dusts                a)      b)                                            ______________________________________                                        Active ingredient according to Tables 2-5                                                              0.1%    1%                                           Talc                    99.9%   --                                            Kaolin                  --      99%                                           ______________________________________                                    

Ready-to-use dusts are obtained by intimate mixing of the carriers withthe active ingredient.

    ______________________________________                                        4. Extruded granules    a)     b)                                             ______________________________________                                        Active ingredient according to Tables 2-5                                                             10%    1%                                             Sodium ligninsulfonate   2%    2%                                             Carboxymethylcellulose   1%    1%                                             Kaolin                  87%    96%                                            ______________________________________                                    

The active ingredient is mixed with the additives and the mixture isground and moistened with water. This mixture is extruded and theextrudate is then dried in a stream of air.

    ______________________________________                                        5. Coated granules                                                            ______________________________________                                        Active ingredient according to Tables 2-5                                                              3%                                                   Polyethylene glycol (molecular weight 200)                                                             3%                                                   Kaolin                   94%                                                  ______________________________________                                    

The finely ground active ingredient is applied uniformly to the kaolin,which has been moistened with polyethylene glycol, in a mixer. Dust-freecoated granules are obtained in this manner.

    ______________________________________                                        6. Suspension concentrate                                                                              a)     b)                                            ______________________________________                                        active ingredient according to Tables 2-5                                                                5%    40%                                          Ethylene glycol           10%    10%                                          Nonylphenol polyethylene glycol                                                                          1%     6%                                          ether (15 mol of ethylene oxide)                                              Sodium ligninsulfonate     5%    10%                                          Carboxymethylcellulose     1%     1%                                          37% aqueous formaldehyde solution                                                                      0.2%   0.2%                                          Silicone oil in the form of a                                                                          0.8%   0.8%                                          75% aqueous emulsion                                                          Water                     77%    32%                                          ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadditives. A suspension concentrate is thus obtained, from whichsuspensions of any desired concentration can be prepared by dilutionwith water.

    ______________________________________                                        7. Salt solution                                                              ______________________________________                                        Active ingredient according to Tables 2-5                                                             5%                                                    Isopropylamine          1%                                                    Octylphenol polyethylene glycol                                                                       91%                                                   ether (78 mol of ethylene oxide)                                              ______________________________________                                    

The compounds of the formula I are employed in unchanged form or,preferably, as compositions together with the auxiliaries customary informulation technology, and are therefore processed in a known mannerfor example to emulsion concentrates, directly sprayable or dilutablesolutions, dilute emulsions, wettable powders, soluble powders, dusts,granules and also capsules in, for example, polymeric substances. Themethods of use, such as spraying, misting, dusting, scattering orpouring, like the nature of the compositions, are chosen according tothe desired effets and the given circumstances.

BIOLOGICAL EXAMPLES EXAMPLE B1 Herbicidal action before emergence of theplants

Plastic pots are filled with expanded vermiculite (density: 0.135 g/cm³,water adsorption capacity: 0.565 l/l). After saturation of thenon-adsorbent vermiculite with an aqueous active ingredient emulsion indeionised water which contains the active ingredients in a concentrationof 70.8 ppm, seeds of the following plants are sown on the surface:Nasturtium officinalis, Agrostis tenuis, Stellaria media and Digitariasanguinalis. The test vessels are then kept in a climatically controlledchamber at a temperature of 20° C., an illumination of about 20 klux anda relative atmospheric humidity of 70%. During a germination phase of 4to 5 days, the pots are covered with transparent material, to increasethe local atmospheric humidity, and watered with deionised water. Afterthe 5th day, 0.5% of a commercially available liquid fertiliser is addedto the watering water. The test is evaluated 12 days after sowing andthe action on the test plants is rated according to the following scale:

    ______________________________________                                        1         plants not germinated or died off completely                        2-3       very severe action                                                  4-6       moderate action                                                     7-8       weak action                                                         9         no action (as untreated control)                                    ______________________________________                                    

                  TABLE B1                                                        ______________________________________                                        Preemergence action:                                                          ______________________________________                                        Concentration of the active ingredient emulsion:                                                       70.8 ppm                                             ______________________________________                                        Active                                                                        ingredient                                                                            Test plants:                                                          No.     Nasturtium  Stellaria                                                                              Agrostis Digitaria                               ______________________________________                                        2.001   3           3        1        3                                       2.002   3           2        2        3                                       2.003   1           2        1        3                                       2.093   2           3        3        3                                       3.003   3           2        1        3                                       3.011   1           2        1        2                                       ______________________________________                                    

EXAMPLE B2 Postemergence herbicidal action (contact herbicide)

After emergence (in the 4- to 6-leaf stage), a number of weed plant,both monocotyledonous and dicotyledonous, were sprayed with an aqueousactive ingredient dispersion in a dosage of 8-500 g of active substanceper hectare, and these were kept at 24°14 26° C. and 45-60% relativeatmospheric humidity. The test is evaluated 15 days after the treatment.

After 3 weeks, the herbicidal action is rated with a nine-level(1=complete destruction, 9=no action) rating scale in comparison with anuntreated control group. Ratings of 1 to 4 (in particular 1 to 3)indicate a good to very good herbicidal action. Ratings of 6 to 9 (inparticular 7 to 9) indicate a good tolerance (in particular by cropplants).

The compounds of the formula I show a potent herbicidal action in thistest.

EXAMPLE B3 Herbicidal action for paddy rice

The aquatic weeds Echinochloa crus galli and Monocharia vag. are sown inplastic beakers (60 cm² surface area, 500 ml volume). After sowing, thebeakers are filled with water to the soil surface. 3 days after sowing,the water level is increased to slightly above the soil surface (3-5mm). The application is carried out 3 days after sowing by spraying thetest substances onto the vessels. The dose used corresponds to an amountof active ingredient of 8-500 g of active substance per hectare. Theplant beakers are then placed in a greenhouse under optimum growingconditions for the rice weeds, i.e. at 25°-30° C. and high atmospherichumidity.

The tests are evaluated 3 weeks after the application. The compounds ofthe formula I damage the weeds in this test.

What is claimed is:
 1. A phenylsulfonamide of the formula ##STR46##wherein X is oxygen, sulfur, SO, or SO₂ ; and wherein R₂ is hydrogen,fluorine, chlorine, bromine, iodine, (X)_(n) R₃, NO₂, NR₄ R₅,--C.tbd.CR₆, ##STR47## or cyano; n is the number 0 or 1; R₃ is C₁ -C₄alkyl or C₁ -C₄ alkyl which is substituted by 1-4 halogen atoms, C₁ -C₃alkoxy or C₁ -C₃ alkylthio; C₂ -C₄ alkenyl C₂ -C₄ alkenyl which issubstituted by 1-4 halogen atoms; R₄ is hydrogen, CH₃ O, CH₃ CH₂ O or C₁-C₃ alkyl; R₅ is hydrogen or C₁ -C₃ alkyl; is hydrogen, methyl or ethyl;and R₇ is hydrogen or methyl.
 2. A phenylsulfonarnide of claim 1 whereinR₂ is hydrogen.
 3. A phenylsulfonamide of claim 2 wherein X is oxygen.4. A phenylsulfonamide of claim 2 wherein X is sulfur.
 5. Aphenylsulfonamide of claim 2 wherein X is SO₂.